Laser marking hologram having a volume hologram with interference fringes using selective irradiation

ABSTRACT

The present invention is provided to enhance security of a volume hologram by recording therein individualized information such as information of character, numerical character, picture pattern, biometric matter and/or the like by irradiating laser light to the volume hologram thereby modifying the same physically or chemically, and is related to a laser marking hologram comprising a volume hologram layer  2  including interference fringes recorded therein, wherein the volume hologram layer  2  includes information of character, numerical character, picture pattern, biometric matter, and/or the like recorded therein having a contrast between an irradiated portion and a non-irradiated portion thereof provided by selectively irradiating laser light  10  to the volume hologram layer  2  in a manner to modify  11  the irradiated portion.

BACKGROUND OF THE INVENTION

The present invention relates to a laser marking hologram and ahologram-oriented laser marking method, and particularly to a hologramexcellent in security and a method for obtaining such a hologram, thehologram having individualized information additionally recorded thereinsuch as information of character, numerical character, picture pattern,biometric matter (fingerprint, face, blood vessel, and the like) and/orthe like by irradiating laser light to a volume hologram therebymodifying the same.

Recently, attention has been directed to a laser engraving method fordirectly engraving personal information into a card or the like. Thelaser engraving technique effectively contributes to constructing amodel of a reliable society system improved in safety and durabilityconcerning prevention of alteration and/or falsification of a card face.It marks personal information, face photograph or the like deeply intoan inside of a card by engraving based on a property change of a cardmaterial itself to thereby complicate counterfeiting, alteration and thelike, thereby enabling realization of a high level security inconjunction with various IC card systems.

Meanwhile, the present applicant has developed and placed on the market,a volume hologram transfer foil capable of realizing a high levelsecurity by transferring a volume hologram, which is apparent concerningan original or imitation at a glance, onto a card. Such a hologram ismass-produced at a high-speed with an identical picture pattern, byusing a hologram master, laser for recording, a hologram photosensitivematerial, and the like.

On the other hand, it has been known, in a relief hologram having areflective layer on a backside, to apply marking to the hologram byselectively irradiating laser light to break the reflective layer, froma Patent Document 1, Patent Document 2 and the like:

[Patent Document 1]

JP-A-11-305667

[Patent Document 2]

JP-A-2002-29185

[Patent Document 3]

JP-A-61-72748

[Patent Document 4]

JP-A-2001-96913

It is typical to modify a card surface layer by an optical processingtechnique such as using laser light, thereby writing personalinformation by a black/white contrast. However, it is impossible tocause the card to have visible security by this technique only, becauseit is difficult to distinguish the written information from thoserecorded by printing, ink jet and the like at a glance.

On the other hand, while volume holograms are produced by theabove-mentioned mass-production scheme, it has been difficult to recordindividualized information since they have no reflective layers likethose of relief holograms. Further, even when a method for recordingsome personal information is realized in a mass-production process suchas based on projection or drawing by laser light, ultraviolet light,white light or the like, it will be impossible to attain an excellentquality in all mass-produced products due to a yield ratio thereof.

Moreover, since mass-produced products including media or carriers andholograms, respectively, each have the same picture pattern in thehologram, it becomes impossible to distinguish a true product from acounterfeit one because a hologram of one product can be detached bysome way from a medium of the same product and then redeployed onto amedium of another product.

SUMMARY OF THE INVENTION

The present invention has been carried out in view of the circumstancesin the related art, and it is therefore an object of the presentinvention to enhance security of a volume hologram by recording thereinindividualized information such as information of character, numericalcharacter, picture pattern, biometric matter and/or the like byirradiating laser light to the volume hologram thereby modifying thesame physically or chemically.

The present invention is configured to directly attain marking in avolume hologram layer which is transferred or laminated onto a mediumsuch as a card and which has hologram interference fringes recordedtherein so as to provide the volume hologram layer with individualizedinformation, thereby disabling reuse of the hologram and achieving ahigher security.

Namely, the present invention resides in a laser marking hologramcomprising a volume hologram layer including interference fringesrecorded therein, characterized in that the volume hologram layerincludes information of character, numerical character, picture pattern,biometric matter, and/or the like recorded therein having a contrastbetween an irradiated portion and a non-irradiated portion thereofprovided by selectively irradiating laser light to the volume hologramlayer in a manner to modify the irradiated portion. Note that the term“laser marking hologram” used in the present invention means a hologramincluding information recorded therein having a contrast by virtue ofthe above described laser marking.

The present invention resides in another laser marking hologramcomprising at least: a protective layer; a volume hologram layercomprising a hologram film medium including interference fringesrecorded therein; and a heat sealing agent or adhesive agent,characterized in that the volume hologram layer includes information ofcharacter, numerical character, picture pattern, biometric matter,and/or the like recorded therein having a contrast between an irradiatedportion and a non-irradiated portion thereof provided by irradiatinglaser light to the volume hologram layer to thereby modify the volumehologram layer.

In the above, it is desirable that the laser for irradiating the laserlight is configured to oscillatingly generate ultrashort pulses within arange of 10 pico-seconds to 10 femto-seconds, or is adapted for anultraviolet region.

Further, it is desirable that the irradiated portion is modified bycondensing the laser light into the volume hologram layer.

It is desirable that the volume hologram layer comprises a photo-polymerincluding at least a photo-polymerizable compound and aphotopolymerization initiator.

In this case, the volume hologram layer may comprise a photo-polymercontaining an inorganic material/organic material for modifying thevolume hologram layer or promoting modification thereof by laser lightirradiation.

In a card having the above described laser marking hologram (i.e., acard with a laser marking hologram), the laser marking hologramincluding information recorded therein by irradiating the laser light tothe volume hologram layer including the interference fringes recordedtherein in a manner to modify the volume hologram layer, the volumehologram layer may include individualized information recorded thereinby irradiation of the laser light.

It is also possible, in such a card with the laser marking hologram,that the volume hologram layer includes the interference fringesrecorded therein as a hologram having a function fordiffracting/transmitting specific light, and that the volume hologramlayer includes individualized information recorded therein byirradiation of the laser light.

The hologram having the function for diffracting/transmitting specificlight may be of any type, and examples thereof include a hologramscatter plate, hologram mirror, and the like each having uniformreflective or scattering surface. Combining the above laser marking witha hologram scatter plate, hologram mirror, or the like allowsinformation having an excellent visibility to be recorded.

The present invention embraces a volume hologram transfer foil,characterized in that the volume hologram transfer foil comprises, in alaminated manner, at least: a substrate; a laser marking hologramcomprising a volume hologram layer, the laser marking hologram includinginformation recorded therein by irradiating laser light to the volumehologram layer including interference fringes recorded therein in amanner to modify the volume hologram layer; and a heat sealing agent oradhesive agent; and also embraces a laser marking hologram-transferredbody comprising a medium having the above described volume hologramtransfer foil transferred thereon.

Also embraced is the laser marking hologram-transferred body, whereinthe medium is in a form of card; wherein the volume hologram layerincludes the interference fringes recorded therein as a hologram havinga function for diffracting/transmitting specific light; and wherein thevolume hologram layer includes individualized information recordedtherein by irradiation of the laser light.

Further, in a laser marking hologram-transferred body having the abovedescribed laser marking hologram, the laser marking hologram includinginformation recorded therein by irradiating the laser light to thevolume hologram layer including the interference fringes recordedtherein in a manner to modify the volume hologram layer, it is possiblethat the volume hologram layer includes individualized informationrecorded therein by irradiation of the laser light.

It is also possible, in a laser marking hologram-transferred body havingthe above described laser marking hologram, the laser marking hologramincluding information recorded therein by irradiating the laser light tothe volume hologram layer including the interference fringes recordedtherein in a manner to modify the volume hologram layer, that the volumehologram layer includes the interference fringes recorded therein as ahologram having a function for diffracting/transmitting specific light,and that the volume hologram layer includes individualized informationrecorded therein by irradiation of the laser light.

Further, the present invention resides in a hologram-oriented lasermarking method for obtaining a hologram including information recordedtherein of character, numerical character, picture pattern, biometricmatter, and/or the like having a contrast, characterized in that themethod comprises the step of: irradiating laser light to a selectedregion of a volume hologram layer including hologram interferencefringes recorded therein so that the interference fringes recorded inthe hologram layer are disordered, thereby enhancing or declining afunction of the interference fringes for diffracting light-beams.

In this case, it is possible that the method further comprises the stepof: establishing a state, which is at or higher than a glass-transitiontemperature of the volume hologram layer, at a light irradiation pointof the volume hologram layer by the laser light, so as to average arefractive index modulation of the volume hologram layer in a manner toprovide a bright/dark contrast between an irradiated portion and anon-irradiated portion.

It is also possible that the method further comprises the step of:realizing a higher energy density at a light irradiation point of thevolume hologram layer by the laser light, so as to control a bondbetween molecules to thereby promote uniformization of the interferencefringes in a manner to provide a bright/dark contrast between anirradiated portion and a non-irradiated portion.

Further, it is possible that the volume hologram layer comprises aphoto-polymer including at least a photo-polymerizable compound and aphotopolymerization initiator.

In that case, the volume hologram layer may comprise a photo-polymercontaining an inorganic material/organic material for modifying thevolume hologram layer or promoting modification thereof by laser lightirradiation.

Moreover, it is desirable that the laser light comprises ultrashortpulses within a range of 10 pico-seconds to 10 femto-seconds, or thelaser is within an ultraviolet region.

It is desirable that the laser light is condensed into the volumehologram layer to thereby modify the irradiated portion.

The present invention resides in a hologram-oriented laser markingmethod for obtaining a hologram including information recorded thereinof character, numerical character, picture pattern, biometric matter,and/or the like having a contrast, characterized in that the methodcomprises the steps of: providing a volume hologram layer includinghologram interference fringes recorded therein; and irradiating laserlight to a selected region of a neighbor layer neighboring to the volumehologram layer in order to migrate a compound contained in the neighborlayer into the volume hologram layer, so that the interference fringesrecorded in the volume hologram layer are disordered, thereby enhancingor declining a function of the interference fringes for diffractinglight-beams.

In this case, it is desirable that the volume hologram layer comprises aphoto-polymer including at least a photo-polymerizable compound and aphotopolymerization initiator.

It is also possible that the laser light is irradiated to the volumehologram layer after the volume hologram layer is included in a transferfoil and then transferred to an adherend, so that the interferencefringes recorded in the volume hologram layer are disordered, therebyenhancing or declining a function of the interference fringes fordiffracting light-beams.

In the present invention, the volume hologram layer includes informationof character, numerical character, picture pattern, biometric matter,and/or the like recorded therein having a contrast between an irradiatedportion and a non-irradiated portion thereof provided by selectivelyirradiating laser light to the volume hologram layer in a manner tomodify the irradiated portion. It is thus possible to recordindividualized information such as two-dimensional personal informationor the like in the hologram by means of a contrast, and/or it ispossible to record two-dimensional personal information or the likeoverlapped with a 3-dimensional image to be reconstructed from thevolume hologram layer, thereby enabling confirmation of an original orimitation of each hologram at a glance, and thereby enabling provisionof individuality to the hologram, to disable reuse of the hologram andthus to obtain a higher security.

Still other objects and advantages of the invention will in part beobvious and will in part be apparent from the specification.

The invention accordingly comprises the features of construction,combinations of element, and arrangement of parts which will beexemplified in the construction hereinafter set forth, and the scope ofthe invention will be indicated in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of an example of a hologramtransfer foil according to the present invention.

FIG. 2 is a schematic cross-sectional view of another example of ahologram transfer foil according to the present invention.

FIG. 3 is a schematic cross-sectional view of still another example of ahologram transfer foil according to the present invention.

FIG. 4 is a schematic cross-sectional view of yet another example of ahologram transfer foil according to the present invention.

FIG. 5 is an explanatory view of an example of a laser light irradiationmethod for marking in the present invention.

FIG. 6 is an explanatory view of a preparation method of a hologrammirror.

FIG. 7 is an explanatory view of a method for fabricating a hologramscatter plate by a one-step shooting method.

FIG. 8 is an explanatory view of a method for fabricating a hologramscatter plate by a two-step shooting method.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Generally, volume holograms are produced based on a large number ofduplications aimed at a large amount of media, and there has beendevised a scheme for providing the holograms with personal informationsuch as by a projection and exposure method upon producing the largenumber of duplications. Further, in a volume hologram comprising aphotopolymer material, it is typically impossible to conduct recordinginto the material when the same is once exposed completely. Thus, therehas not been conventionally devised a method for recording personalinformation into a hologram material layer which has been completed inexposure and worked into a sample form.

The present invention resides in a laser marking hologram having avolume hologram layer including hologram interference fringes recordedtherein by laser interference, characterized in that laser light isirradiated to the volume hologram layer to corrupt shapes of theinterference fringes (i.e., disorder the interference fringes) recordedin the hologram layer, thereby enhancing (which exemplarily means towiden a diffraction range for more brightness) or declining the functionof them for diffracting light-beams.

The volume hologram layer including hologram interference fringesrecorded therein, comprises innumerable interference fringes, andincident light is diffracted to a certain angle by the interferencefringes. It is possible to record information, by using laser light tothereby average or disorder a refractive index modulation of thepreviously recorded interference fringes, in a manner to attain abright/dark contrast between an irradiated portion and a non-irradiatedportion. For example, adoption of pulse laser on the order of ns(nano-second) enables, at a laser light irradiated point, establishmentof a state at a temperature higher than a glass transition point of thevolume hologram layer, thereby conducting thermal modification for thematerial itself. At this time, condensation of laser light-beams enablesrealization of a high heat spot at a higher efficiency. The heat thereofis utilized to average a refractive index modulation, thereby enablingprovision of a bright/dark contrast between an irradiated portion and anon-irradiated portion. Further, adoption of pulse laser on the order offs (femto-second) enables an extremely high energy density at a laserlight irradiated point, in a manner to conduct control such as cuttingof a bond between molecules without giving heat thereto, by virtue of soshortened pulses. This promotes uniformization of interference fringes,thereby enabling realization of a contrast between an irradiated portionand a non-irradiated portion. Herein, uniformization of interferencefringes means to decrease contrasts (brightness and darkness) of theinterference fringes themselves to thereby average the refractiveindexes.

Here, since the glass-transition temperature of the volume hologramlayer of the present invention is 80° C. to 90° C., it is enough for alaser light irradiated point to be in a high heat state higher than 90°C. Note that the present invention uses a glass-transition temperaturewhich is a value measured by a solid viscoelasticity analyzer RSA-IImade by RHEOMETRICS LTD., under the following conditions. There weremeasured a dynamic storage elastic modulus (E′) and a dynamic losselastic modulus (E″), and there was adopted, as a glass-transitiontemperature, a peak temperature of a loss tangent defined by E″/E′.

The present invention will be concretely explained hereinafter. Thepresent invention embraces a volume hologram oriented resin composition,a volume hologram layer formed by using it, and a hologram transferfoil. These will be explained hereinafter item by item.

There will be firstly explained a laser marking hologram orientedmaterial of the present invention. Usable as a laser marking hologramoriented material are conventionally known volume hologram recordingmaterials. Concretely, examples thereof include a silver salt sensitivematerial, gelatin dichromate, photo-cross-linking polymer,photo-polymer, and the like. Particularly, photo-polymer is excellent inmass-productiveness as compared with other materials, since it allowsfor fabrication of a volume hologram only by a dry process.

There will be concretely explained photo-polymer-materials.

The photo-polymer to be used as a laser marking hologram orientedmaterial of the present invention includes at least one kind ofphoto-polymerizable compound and a photopolymerization initiator.

It is possible to obtain a desired laser marking hologram by recording,by the marking method of the present invention, information such asinformation of character, numerical character, picture pattern,biometric matter and/or the like in a volume hologram to be obtained bysuch a photo-polymer.

There will be explained constituent materials of such a volume hologramrecording photo-polymer.

1. Photo-Polymerizable Compound

Photo-polymerizable compounds to be used in the present invention willbe explained. Photo-polymerizable compounds in the present invention maybe radical photo-polymerizable compounds or cationic photo-polymerizablecompounds. There will be explained hereinafter radicalphoto-polymerizable compounds and cationic photo-polymerizable compoundsin a separated manner.

a. Radical Photo-Polymerizable Compound

Radical photo-polymerizable compounds to be used in the presentinvention are not particularly limited insofar as the same arepolymerized by an effect of active radicals generated from a radicalphotopolymerization initiator to be described later upon forming avolume hologram by a volume hologram oriented resin composition of thepresent invention, and it is possible to use a compound having at leastone ethylenically unsaturated double bond capable of additionpolymerization. Examples thereof include unsaturated carboxylic acids,salts of unsaturated carboxylic acids, esters of unsaturated carboxylicacids and aliphatic polyhydric alcohol compounds, amide compounds ofunsaturated carboxylic acids and aliphatic polyvalent amine compounds,and the like. There will be described concrete examples of monomers forthe above-mentioned esters of unsaturated carboxylic acids and aliphaticpolyhydric alcohol compounds.

Examples of acrylic esters include ethylene glycol diacrylate,triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethyleneglycol diacrylate, propylene glycol diacrylate, neopentyl glycoldiacrylate, trimethylolpropane triacrylate, trimethylolpropanetri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanedioldiacrylate, 1,4-cyclohexanediol diacrylate, tetraethyleneglycoldiacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythri.tol diacrylate,dipentaerythritol triacrylate, dipentaerythritol tetraacrylate,dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitoltetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,tri(acryloyloxyethyl)isocyanurate, polyester acrylate oligomer,2-phenoxyethyl acrylate, phenolethoxylate monoacrylate,2-(p-chlorophenoxy)ethyl acrylate, p-chlorophenyl acrylate, phenylacrylate, 2-phenylethyl acrylate, bisphenol A (2-acryloxyethyl) ether,ethoxylated bisphenol A diacrylate, 2-(1-naphthyloxy)ethyl acrylate,o-biphenyl methacrylate, 9,9-bis(4-acryloxydiethoxyphenyl)fluorene,9,9-bis(4-acryloxytriethoxyphenyl)fluorene,9,9-bis(4-acryloxydipropoxyphenyl)fluorene,9,9-bis(4-acryloxyethoxy-3-methylphenyl)fluorene,9,9-bis(4-acryloxyethoxy-3-ethylphenyl)fluorene,9,9-bis(4-acryloxyethoxy-3,5-dimethyl)fluorene, and the like.

It is also possible to use sulfur-containing acrylic compounds disclosedin the Patent Document 3. Examples thereof include4,4′-bis(β-acryloyloxyethylthio)diphenylsulfone,4,4′-bis(β-acryloyloxyethylthio)diphenyl ketone,4,4′-bis(β-acryloyloxyethylthio)-3,3′,5,5′-tetrabromo diphenyl ketone,2,4-bis(β-acryloyloxyethylthio)dipenyl ketone, and the like.

Further, examples of methacrylic esters include those compounds whichare provided by changing “acrylate” to “methacrylate”, “acryloxy” to“methacryloxy”, and “acryloyl” to “methacryloyl”, respectively, in thecompound names exemplified by the above acrylic esters.

Moreover, the radical photo-polymerizable compounds may be used solely,or combinedly in two or more kinds.

b. Cationic Photo-Polymerizable Compound

Cationic photo-polymerizable compounds to be used in the presentinvention are cationic polymerized by Broensted acid or Lewis acidgenerated by decomposition of a cationic photo-polymerization initiatorto be described later, subject to energy irradiation. Examples thereofinclude cyclic ethers such as having epoxy ring, oxetane ring and thelike; thioethers; vinyl ethers, and the like.

Examples of compounds containing an epoxy ring include polyalkyleneglycol diglycidyl ether, bisphenol A diglycidyl ether, glycerintriglycidyl ether, diglycerol triglycidyl ether, diglycidylhexahydrophthalate, trimethylolpropanediglycidyl ether, allylglycidylether, phenylglycidyl ether, cyclohexene oxide, and the like.

Moreover, the cationic photo-polymerizable compounds may be used solely,or combinedly in two or more kinds.

Furthermore, it is possible to combine one or two or more kinds of theabove-mentioned radical photo-polymerizable compounds with one or two ormore kinds of the above-mentioned cationic photo-polymerizablecompounds, and to use them.

Here, formation of a volume hologram by a volume hologram oriented resincomposition of the present invention is conducted by irradiating laserin a shape of an intended image to thereby polymerize a radicalphoto-polymerizable compound, for example, and thereafter irradiating anenergy to the whole surface of the composition to thereby polymerizeuncured substances such as a cationic photo-polymerizable compound. Notethat it is typical for laser or the like upon formation of the image andthe energy to be irradiated over the whole surface that they aredifferent in wavelength, and it is desirable that the cationicphoto-polymerizable compounds to be used in the present invention arenot polymerized by the laser for formation of an image, for example.

Further, such cationic photo-polymerizable compounds are desirably to beliquid at an ordinary temperature, from a standpoint that polymerizationof the radical photo-polymerizable compounds is desirably conductedwithin a composition having a relatively low viscosity.

c. Others

Photo-polymerizable compounds to be used in the present invention areeach desirably used at 10 to 1,000 parts by weight, preferably 10 to 300parts by weight, relative to 100 parts by weight of a binder resin to bedescribed later.

Here, the volume hologram is configured to form an image, bypolymerizing a photo-polymerizable compound by laser light or by lighthaving an excellent coherency to thereby form interference fringes.Thus, in case that the volume hologram oriented resin compositioncontains both a radical photo-polymerizable compound and a cationicphoto-polymerizable compound, these compounds are selected and used in amanner to have refractive indexes different from each other where eithermay have a larger refractive index. It is desirable in the presentinvention that an averaged refractive index of a radicalphoto-polymerizable compound is larger than that of a cationicphoto-polymerizable compound particularly from a standpoint of amaterial selectivity, and concretely, the former averaged refractiveindex is larger than the latter by 0.02 or more. This is because, whendifferences between averaged refractive indexes of the radicalphoto-polymerizable compound and cationic photo-polymerizable compoundare smaller than the above value, refractive index modulation becomesinsufficient to possibly complicate formation of high-definition image.The term “averaged refractive index” refers to an averaged value ofrefractive indexes to be measured for a polymer after polymerization ofa cationic photo-polymerizable compound or radical photo-polymerizablecompound. Further, refractive indexes noted in the present inventionhave values measured by an Abbe refractometer.

2. Photopolymerization Initiator

There will be next explained photopolymerization initiators to be usedin the present invention. Photopolymerization initiators in the presentinvention are different in type depending on the above-mentionedphoto-polymerizable compounds. Namely, it is necessary to select aradical photopolymerization initiator as a photopolymerization initiatorwhen the photo-polymerizable compound is a radical photo-polymerizablecompound, and to select a cationic photo-polymerization initiator as aphotopolymerization initiator when the photo-polymerizable compound is acationic photo-polymerizable compound. There will be explained radicalphotopolymerization initiators and cationic photo-polymerizationinitiators in a separated manner.

a. Radical Photopolymerization Initiator

Radical photopolymerization initiators to be used in the presentinvention are not particularly limited insofar as the same are capableof generating active radicals such as by laser to be irradiated uponforming a volume hologram by a volume hologram oriented resincomposition of the present invention, thereby polymerizing the radicalphoto-polymerizable compound. Examples thereof include imidazolederivatives, bisimidazole derivatives, N-arylglycine derivatives,organic azide compounds, titanocenes, aluminate complexes, organicperoxides, N-alkoxypyridinium salts, and thioxanthone derivatives.Concretely, examples thereof include1,3-di(tert-butyldioxycarbonyl)benzophenone,3,3′,4,4′-tetrakis(tert-butyldioxycarbonyl)benzophenone,3-phenyl-5-isooxazolone, 2-mercaptobenzimidazole,bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one(trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals,Inc.), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184,manufactured by Ciba Specialty Chemicals, Inc.),2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one (tradename: Irgacure 369, manufactured by Ciba Specialty Chemicals, Inc.), andbis(q5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium(trade name: Irgacure 784, manufactured by Ciba Specialty Chemicals,Inc.), and the like.

b. Cationic Photo-Polymerization Initiator

Cationic photo-polymerization initiators to be used in the presentinvention are not particularly limited insofar as the same generateBroensted acid or Lewis acid by energy irradiation to thereby polymerizethe cationic photo-polymerizable compounds, respectively. In case thatthe volume hologram oriented resin composition contains both a radicalphoto-polymerizable compound and a cationic photo-polymerizablecompound, it is desirable that the cationic photo-polymerizable compoundis not sensitive to laser or to light having an excellent coherencywhich polymerizes the radical photo-polymerizable compound, but isphotoactivated by an energy to be subsequently irradiated to the wholesurface of the composition. This is because, the cationicphoto-polymerizable compound is then allowed to be present in asubstantially unreacted state upon polymerization of the radicalphoto-polymerizable compound, thereby enabling obtainment of a largerrefractive index modulation in the resultant volume hologram.

Concrete examples thereof include sulfonates, imidesulfonates,dialkyl-4-hydroxysulfonium salts, p-nitrobenzyl arylsulfonate,silanol-aluminum complexes, (η6-benzene) (η5-cyclopentadienyl) iron(II), and the like. Further usable are benzoin tosylate,2,5-dinitrobenzyltosylate, N-tosylphthalic imide, and the like.

c. Others

Examples of initiators usable as both a radical photopolymerizationinitiator and a cationic photo-polymerization initiator in the presentinvention, include aromatic iodonium salts, aromatic sulfonium salts,aromatic diazonium salts, aromatic phosphonium salts, triazinecompounds, iron arene complexes, and the like. Concretely, examplesthereof include iodonium salts such as chloride, bromide, borofluoride,hexafluorophosphate, hexafluoroantimonate or the like of iodoniums, suchas diphenyliodonium, ditolyliodonium, bis(p-t-butylphenyl)iodonium,bis(p-chlorophenyl)iodonium, and the like; sulfonium salts such aschloride, bromide, borofluoride, hexafluorophosphate, fluoroantimonateor the like of sulfoniums, such as triphenylsulfonium,4-t-butyltriphenylsulfonium, tris(4-methylphenyl)sulfonium, and thelike; and 2,4,6-substituted-1,3,5-triazine compounds such as2,4,6-tris(trichloromethyl)-1,3,5-triazine,2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine,2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, and the like.

Further, the photopolymerization initiators may be used solely, orcombinedly in two or more kinds.

Moreover, the photopolymerization initiator is desirably used at 0.1 to20 parts by weight, preferably 5 to 15 parts by weight, relative to 100parts by weight of a binder resin to be described later.

3. Additives

There will be explained additives which can be added to a volumehologram oriented resin composition of the present invention.

a. Sensitizing Pigment

In the present invention, it is desirable that the volume hologramoriented resin composition contains a sensitizing pigment. This isbecause, although the photo-polymerizable compound andphotopolymerization initiator are often activated by ultraviolet light,addition of a sensitizing pigment makes them to be activated even byvisible light, thereby enabling interference fringes to be recorded byvisible laser light.

Such sensitizing pigments are selected in consideration of wavelengthsof laser light-beams to be used upon recording of interference fringes,without limited thereto. Exemplarily usable are a thiopyrylium saltbased pigment, merocyanine based pigment, quinoline based pigment,styrylquinoline based pigment, coumarin based pigment, ketocoumarinbased pigment, thioxanthene based pigment, xanthene based pigment,oxonol based pigment, cyanine based pigment, rhodamine based pigment,pyrylium based pigment, cyclopentanone based pigment, cyclohexanonebased pigment, and the like.

Examples of the merocyanine based pigment and cyanine based pigmentinclude 3,3′-dicarboxylethyl-2,2′-thiocyanine bromide,1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide,1,3′-diethyl-2,2′-quinothiacyanine iodide, and3-ethyl-5-[(3-ethyl-2(3H)-benzothiazolidene)ethylidene]-2-thioxo-4-oxazolidine,and the like.

Examples of the coumarin based pigment and ketocoumarin based pigmentinclude 3-(2′-benzimidazol)-7-N,N′-diethylaminocoumarin,3,3′-carbonylbis(7-diethylaminocoumarin), 3,3′-carbonylbiscoumarin,3,3′-carbonylbis(5,7-dimethoxycoumarin), and3,3′-carbonylbis(7-acetoxycoumarin), and the like.

Since a sensitizing pigment having absorption wavelengths in a visiblelight range is required to have a higher transparency upon usage thereofas an optical element, for example, it is desirable for a sensitizingpigment to become colorless such as by heating or ultraviolet lightirradiation after a process of recording interference fringes.Preferably used as such a sensitizing pigment are the above-mentionedcyanine based pigments.

Further, it is desirable to use a sensitizing pigment at 0.01 to 10parts by weight, preferably 0.01 to 2 parts by weight, relative to 100parts by weight of a binder resin to be described later.

b. Binder Resin

In the present invention, it is desirable that the volume hologramoriented resin composition contains a binder resin. This is because,containment of a binder resin enables improvement of a film-formingability and a film thickness uniformity, and enables stabilized presenceof recorded interference fringes.

Examples of such a binder resin include: polymethacrylate orpartially-hydrolyzed products thereof; polyvinyl acetate or hydrolyzedproducts thereof; polyvinyl alcohol or partially-acetalized productsthereof; triacetylcellulose, polyisoprene, polybutadiene,polychloroprene, silicone rubber, polystyrene, polyvinyl butyral,polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinatedpolypropylene, poly-N-vinylcarbazole or derivatives thereof;poly-N-vinylpyrrolidone or derivatives thereof; copolymer of styrene andmaleic anhydride or semi-esterified products thereof. It is alsopossible to use copolymers obtained by copolymerization of at least onekind of monomer selected from a group of acrylic acid, acrylic esters,methacrylic acid, methacrylic esters, acrylamide, acrylonitrile,ethylene, propylene, vinyl chloride, vinyl acetate, and the like. It isfurther possible to use copolymers obtained by copolymerization ofmonomers each having a thermosetting or photo-curable functional groupat a side-chain. It is also possible to use the binder resin(s), solely,or combinedly in two or more kinds.

Also usable as a binder resin is a setting resin of an oligomer type.Examples thereof include epoxy compounds to be produced by acondensation reaction of: any one of various phenolic compounds such asbisphenol A, bisphenol S, novolak, o-cresol novolak, p-alkylphenolnovolak; and epichlorohydrin.

Usable as the binder resin is an organic-inorganic hybrid polymerutilizing a sol-gel reaction. Examples thereof include a copolymer of avinyl monomer and an organo-metallic compound having a polymerizablegroup represented by the following general formula (1):R_(m)M(OR′)_(n)  (1)

(wherein M represents a metal such as Si, Ti, Zr, Zn, In, Sn, Al, Se, orthe like; R represents a vinyl group or (meth)acryloyl group having 1 to10 carbon atoms; R′ represents an alkyl group having 1 to 10 carbonatoms; and m+n is a valence of the metal M).

Examples of the organo-metallic compound in case of usage of Si as themetal M, include vinyltriethoxy-silane, vinyltrimethoxy-silane,vinyltributoxy-silane, vinyltriallyloxy-silane, vinyltetraethoxy-silane,vinyltetramethoxy-silane, acryloxy-propyltrimethoxy-silane,methacryloxy-propyltrimethoxy-silane, and the like.

Examples of the vinyl monomer include acrylic acid, acrylates,methacrylic acid, methacrylates, and the like.

Here, the volume hologram is formed by recording interference fringestherein as a refractive index modulation or transmittivity modulation.It is thus desirable that a binder resin and a photo-polymerizablecompound have a larger refractive index difference therebetween. In thepresent invention, it is also possible to add an organo-metalliccompound represented by the following general formula (2) into thevolume hologram oriented resin composition, so as to increase arefractive index difference between a binder resin and aphoto-polymerizable compound:M(OR″)_(k)  (2)

(wherein M represents a metal such as Ti, Zr, Zn, In, Sn, Al, Se, or thelike; R″ represents an alkyl group having 1 to 10 carbon atoms; and “k”is a valence of the metal M).

Addition of the compound represented by the formula (2) to the volumehologram oriented resin composition; forms a network structure with thebinder resin by a sol-gel reaction in the presence of water and an acidcatalyst, thereby exhibiting an effect to not only increase a refractiveindex of the binder resin but also improve stiffness and heat resistanceof the film. It is thus desirable to use a metal M having a higherrefractive index so as to increase a refractive index difference betweenthe binder resin and the photo-polymerizable compound.

The binder resin is used, typically in a range of 15 to 50 wt %,desirably in a range of 20 to 40 wt %, in the volume hologram orientedcomposition.

4. Compound Capable of Laser Marking

In addition to the above materials, addition of a compound is possiblewhich promotes modification by laser light irradiation. Only, this isnot indispensable, depending on a kind of modification (to be describedlater).

Examples of such compounds include inorganic and/organic ones.

Although various materials such as flaky or particulate ones are usable,it is desirable to use those having sizes smaller than wavelengths(recording wavelengths) of laser or the like to be used upon recording ahologram image. For example, considering an averaged particle size asthe size, averaged particle sizes larger than recording wavelengths mayoccasionally affect formation of a hologram image. Here, in case offabrication of a color hologram, for example, it is typical to selectfine particles having particle sizes smaller than the shortestwavelength among recording wavelengths to be used. It is thus enough toappropriately select an averaged particle size of materials, dependingon recording wavelengths to be used.

As a concrete averaged particle size, it is desirably within a range of50 nm to 700 nm, and particularly 50 nm to 400 nm. This is because,averaged particle sizes smaller than the above range lead to complicatedmanufacturing and makes it difficult to provide brittleness uponformation of a volume hologram layer by using the volume hologramoriented resin composition of the present invention, while averagedparticle sizes larger than the above range may occasionally affectformation of a hologram image.

The averaged particle size mentioned herein is typically used torepresent a granularity of particles, and is a value measured by a lasermethod. The laser method is configured to measure an averaged particlesize, granularity distribution, and the like, by dispersing particles ina solvent, by narrowing scattered light obtained by irradiating laserlight to the dispersion solvent, and by conducting calculation. Theabove averaged particle size is a value measured by a particle sizeanalyzer MICRO TRACK UPA Model-9230 manufactured by Leeds & Northrup, asa particle size measuring device.

Usable as concrete inorganic materials are synthesized or natural mica,talc, kaolin, glass flake, silica, and various metal oxides such astitanium dioxide, zinc oxide, zirconium dioxide, chromium oxide,nickel-oxide, copper oxide, cobalt oxide, iron oxide, and the like.Further, examples thereof include various alloy materials including Fe,Co, Ni as main components, such as Fe—Co, Fe—Ni, Fe—Co—Ni, Co—Ni,Fe—Mn—Zn, Fe—Ni—Zn, Fe—Co—Ni—Cr, Fe—Co—Ni—P, Fe—Co—B, Fe—Co—Cr—B,Fe—Co—V, and the like. These materials embrace those including elementsadded therein such as Al, Si, Ti, Cr, Mn, Mg, P, and the like for thepurpose of providing or improving various properties.

Examples of concrete organic materials include photochromic compoundseach having a structure to be changed by a light energy, such aschromene based compounds, spirooxazine based compounds, spiropyran basedcompounds, fulgide based compounds, azobenzene based compounds, and thelike.

It is also possible to use an inorganic-organic composite material, suchas titanium dioxide, mica, and the like having a surface coated withanthracene or pentaerythritol, as disclosed in the Patent Document 4.

The compounds are desirably contained in the volume hologram orientedresin composition, within a range of 1 to 30 wt %, preferably in a rangeof 5 to 20 wt %. This is because, contents of the compounds less thanthe above range lead to deteriorated effects of laser marking, whilecontents exceeding the above range occasionally make it difficult tokeep a strength, transparency, and hologram recording ability of thevolume hologram layer.

Other compounds, which are added into a hologram layer to therebypromote modification by laser light irradiation, include the following:

Microcapsule

There is set a capsule melting temperature to be higher than a hologramfabrication process temperature (150° C., for example). Capsules are tobe filled with a compound: plasticizer, photo-polymerizable compound,which disorders or breaks interference fringes. Hollow particles (suchas hollow silica, hollow acrylic resin) having internal void cavitiesare possible.

Compound adapted to foam (form voids) by heat or light upon laserirradiation

Examples thereof include a thermal polymerization initiator such asAIBN. Formation of voids obtains a larger refractive index modulation,and achieves marking. Possibility of photopolymerization initiator isalso conceivable.

Substance (photochromic molecule, metal chelate) to be bonded to binderframe

Usage of an organic-inorganic hybrid polymer as a binder possiblyenables an effective marking without using a specific additive forpromotion of marking.

There will be explained formation of a volume hologram layer of thepresent invention.

Upon formation of a volume hologram layer in the present invention, thevolume hologram oriented resin composition is firstly coated onto anintended substrate film, for example, by typical coating means, anddried as required, to establish a volume hologram formation layer. Thevolume hologram formation layer may be formed by injecting a volumehologram oriented resin composition into between two glass plates, forexample. Next, the above volume hologram formation layer is exposed tolaser light to be typically used for a holography exposure apparatus orto light having an excellent coherency (such as light having wavelengthsof 300 nm to 1,200 nm), to thereby polymerize the photo-polymerizablecompound, thereby recording interference fringes of an intended image inthe layer. This forms the volume hologram layer.

It is possible to use a solvent as required, upon coating the volumehologram oriented resin composition. Examples of usable solvents includeacetone, methylethyl ketone, methylisobutyl ketone, cyclohexanone,benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methylcellosolve, ethyl cellosolve, methyl cellosolve acetate, ethylcellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane,dichloromethane, chloroform, methanol, ethanol, isopropanol, and thelike. These solvents may be used solely, or mixedly in two or morekinds.

Further, usable for a coating method for the volume hologram orientedresin composition are a spin coater, gravure coater, comma coater, barcoater, and the like.

The coating amount of the volume hologram oriented resin composition isappropriately selected depending on usage and/or kind of the volumehologram layer, and is typically within a range of 1 g/m² to 100 g/m²,preferably within a range of 2 g/m² to 40 g/m², while the film thicknessof the volume hologram formation layer is typically within a range of 1μm to 100 μm, and particularly 2 μm to 40 μm. Further, the filmthickness of a volume hologram layer to be formed by curing the volumehologram oriented resin composition, is preferably within a range of 1to 100 μm, and particularly 10 to 40 μm.

The above volume hologram formation layer is exposed to laser light tobe typically used for a holography exposure apparatus or to light havingan excellent coherency (such as light having wavelengths of 300 nm to1,200 nm), to thereby polymerize the photo-polymerizable compound,thereby recording interference fringes of an intended image in thelayer. Usable as the laser light are visible laser such as argon ionlaser (458 nm, 488 nm, 514.5 nm), kryton ion laser (647.1 nm),helium-neon laser (633 nm), YAG laser (532 nm), and the like.

Usable as the method for recording interference fringes of an image is aconventionally known one. For example, interference fringes of an imagecan be recorded in the volume hologram formation layer, by closelycontacting a master with the volume hologram formation layer, and byconducting interference exposure from a substrate film side by visiblelight or ionizing radiation such as ultraviolet light or electron beam.The interference fringes may be any holograms without limitation insofaras they are interference fringes as holograms each having a function fordiffracting/transmitting specific light, and examples thereof include ahologram scatter plate, hologram mirror, and the like having a uniformreflective or scattering surface. Combining the above laser marking witha hologram scatter plate, hologram mirror, or the like allowsinformation having an excellent visibility to be recorded.

For fabrication of a hologram mirror as shown in FIG. 6, closelycontacted with or arranged near a reflecting mirror 16 is a volumehologram material 15 comprising the above volume hologram recordingphoto-polymer, and coherent light 17 at a predetermined wavelength isinjected into the volume hologram material 15 from a side opposite tothe mirror so as to be interfered, within the volume hologram material15, with reflected light 18 transmitted through the volume hologrammaterial 15 and regularly reflected by the reflecting mirror 16, therebyrecording a hologram mirror within the volume hologram material 15.

Further, while several methods are present for fabricating a hologramscatter plate, FIG. 7 shows a one-step shooting method and FIG. 8 showsa two-step shooting method. In the one-step shooting method of FIG. 7,there is arranged a volume hologram material 21 comprising the volumehologram recording photo-polymer at a position previously determined asa diffuse reflection area relative to a scatter plate 20 such as frostedglass; and the scatter plate 20 is illuminated from its backside bycoherent light 22 at a predetermined wavelength bifurcated from a singlelight source in a manner that scattered light 24 exiting from a frontsurface of the scatter plate 20 is injected as object beams into thevolume hologram material 21, and simultaneously therewith, referencebeams 23 comprising another coherent light 23 at the predeterminedwavelength bifurcated from the same light source are injected into thevolume hologram material 21 in a manner to advance in a directionopposite to incident light to be assumed in a hologram scatter plate; sothat the volume hologram material 21 is brought to have the hologramscatter plate recorded therein.

In the two-step shooting method of FIG. 8, there is arranged atransmission-type hologram dry plate 25 as shown in FIG. 8( a) at aposition previously determined as a diffuse reflection area relative toa scatter plate 20 such as frosted glass; and the scatter plate 20 isilluminated from its backside by coherent light 22 at a predeterminedwavelength bifurcated from a single light source in a manner thatscattered light 24 exiting from a front surface of the scatter plate 20is injected as object beams into the transmission-type hologram dryplate 25, and simultaneously therewith, reference beams 26 comprisinganother coherent light 26 at the predetermined wavelength bifurcatedfrom the same light source are injected into the transmission-typehologram dry plate 25 from the same side as the scattered light 24 at anarbitrary angle; so that the transmission-type hologram dry plate 25 isbrought to have a transmission-type hologram recorded therein as a firsthologram.

Next, as shown in FIG. 8( b), this first hologram is numbered as 27 andarranged at a position of the original transmission-type hologram dryplate 25, and there is newly arranged a volume hologram material 30comprising the above volume hologram recording photo-polymer at aposition of the scatter plate 20; there is irradiated reconstructiveillumination light 28, which is provided from a side opposite to thecoherent light 26 upon recording and which has the same wavelength asthe coherent light 26, onto the hologram 27 so as to cause a real imageof the hologram 27 to be formed near a position of the volume hologrammaterial 30 (i.e., position of the scatter plate 20 in FIG. 8( a)),thereby injecting diffracted light 29 from the hologram 27 as objectbeams into the volume hologram material 30; and simultaneouslytherewith, reference beams 31 are injected into the volume hologrammaterial 30 from an opposite side in a manner to advance in a directionopposite to incident light to be assumed in a hologram scatter plate; sothat the volume hologram material 30 is brought to have the hologramscatter plate recorded therein as a second hologram. This method allowsfor fabrication of a hologram scatter plate having an observation arearestricted within a range of the first hologram 27. Further, also ahologram duplicated by closely contacting with this hologram as amaster, is provided as a hologram scatter plate keeping a diffractingdirection (scattering direction) of the master. It is also possible toutilize a 3-dimensional object image such as a model, by the two-stepshooting method in the same manner as that shown in FIG. 8. This is alsoapplicable to a scatter plate pattern.

After the interference exposure as described above, it is possible toappropriately conduct a treatment such as whole surface exposure byultraviolet light or heating, for promotion of refractive indexmodulation, and completion of a polymerization reaction of aphoto-polymerizable compound and the like.

There will be explained a hologram transfer foil of the presentinvention.

The hologram transfer foil of the present invention comprises the volumehologram layer, a substrate film, and a thermo-sensitive adhesive layer,characterized in that the volume hologram layer is formed on thesubstrate film, and the thermo-sensitive adhesive layer is formed on thevolume hologram layer.

According to the present invention, the hologram transfer foil has thevolume hologram layer of the present invention, and there can beprovided a high level security by providing the volume hologram layerwith information by the laser marking in the above-mentioned manner.

As shown in FIG. 1, the hologram transfer foil of the present inventionincludes a substrate film 1, a volume hologram layer 2 formed on thesubstrate film 1, and a thermo-sensitive adhesive layer 3 formed on thevolume hologram layer 2.

In the hologram transfer foil of the present invention, thethermo-sensitive adhesive is contacted with an adherend and heat isapplied from the substrate film side, thereby enabling the volumehologram layer to be adhered to the adherend through thethermo-sensitive adhesive, and enabling the volume hologram layer to betransferred onto the adherend. According to the present invention, it ispossible at this time to transfer the above-mentioned volume hologramlayer onto the adherend only at an intended portion because the volumehologram layer has an excellent foil cutting property, thereby enablingachievement of the hologram transfer foil applicable to various usage.

Such transference can be conducted as shown in FIG. 2, for example: byoverlapping the hologram transfer foil onto an adherend 6 fortransference of hologram such that the thermo-sensitive adhesive layer 3is contacted with a surface of the adherend; by exemplarily applying,from the substrate film side, heat and pressure by a heatable die 7 to aportion where the hologram is to be transferred, to thereby meltinglyadhere the thermo-sensitive adhesive layer 3 to the adherend; and bysubsequently delaminating the substrate film 1 therefrom.

There will be explained other configurations of the hologram transferfoil.

1. Substrate Film

The substrate film to be used for the hologram transfer foil of thepresent invention is to be formed thereon with the above-mentionedvolume hologram layer, and there is conducted thermal transference fromthis substrate film side upon transferring the volume hologram layeronto an adherend. Thus, the substrate film is not particularly limited,insofar as the same can be formed thereon with the volume hologram layerand has a resistance to heat and pressure to be applied thereto uponthermal transference. For example, it is possible to use a transparentresin film such as a polyethylene film, polypropylene film, polyethylenefluoride-based film, polyvinylidene fluoride film, polyvinyl chloridefilm, polyvinylidene chloride film, ethylene-vinyl alcohol copolymerfilm, polyvinyl alcohol film, polymethyl methacrylate film, polyethersulfone film, polyetherether ketone film, polyamide film,tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film, apolyester film such as a polyethylene terephthalate film, or a polyimidefilm.

Further, although the thickness of such a substrate film isappropriately selected depending on usage and type of the hologramtransfer foil, it is typically within a range of 2 μm to 200 μm, andpreferably 10 μm to 50 μm.

2. Thermo-Sensitive Adhesive Layer

There will be explained the thermo-sensitive adhesive layer to be usedin the hologram transfer foil of the present invention. Thethermo-sensitive adhesive layer is a layer, which is formed at a surfaceof the hologram transfer foil at an opposite side to the substrate film,and which is closely contacted with the adherend and exemplarily heatedupon transferring the volume hologram layer onto the adherend by thermaltransference, thereby adhering the volume hologram layer to theadherend.

Usable as such a thermo-sensitive adhesive layer are thermoplasticresins such as an ethylene-vinyl acetate copolymer resin (EVA),polyamide resin, polyester resin, polyethylene resin, ethylene-isobutylacrylate copolymer resin, butyral resin, polyvinyl acetate and itscopolymer resin, cellulose-based resin, polymethyl methacrylate resin,polyvinyl ether-based resin, polyurethane resin, polycarbonate resin,polypropylene resin, epoxy resin, phenol resin, styrene butadienestyrene block copolymer (SBS), styrene isoprene styrene block copolymer(SIS), styrene ethylene butylene styrene block copolymer (SEBS), styreneethylene propylene, and styrene block copolymer (SEPS). Among them, itis desirable to use one which is heat sealable at a temperature of 180°C. or lower, and it is desirable to use an ethylene-vinyl acetatecopolymer resin (EVA) having an acetic acid content of 25% or more.Further, the thermo-sensitive adhesive layer of the resin may be coloredas required.

3. Hologram Transfer Foil

There will be explained the hologram transfer foil of the presentinvention. The hologram transfer foil of the present invention is notlimited in terms of a constitution and the like thereof, insofar as itincludes the volume hologram layer, the substrate film, and thethermo-sensitive adhesive layer, in a manner that the volume hologramlayer is formed on the substrate film, and the thermo-sensitive adhesivelayer is formed on the volume hologram layer. Unlike these layers, thehologram transfer foil may include, as shown in FIG. 3, a substrate film1, a delamination layer 4 formed on the substrate film 1, a volumehologram layer 2 formed on the delamination layer 4, and athermo-sensitive adhesive layer 3 formed on the volume hologram layer 2.Further, the hologram transfer foil may include, as shown in FIG. 4, asubstrate film 1, a volume hologram layer 2 formed on the substrate film1, a reflective layer 5 formed on the volume hologram layer 2, and athermo-sensitive adhesive layer 3 formed on the reflective layer 5.

The delamination layer is configured to enable facilitated delaminationof the substrate film from the volume hologram layer upon transferringthe volume hologram layer onto an adherend by using the hologramtransfer foil, and usable examples thereof include one kind or combinedtwo or more kinds selected from acrylic resins, vinyl chloride-vinylacetate copolymer resin, polyester resin, polymethacrylate resin,polyvinyl chloride resin, cellulose resin, silicone resin, chlorinatedrubber, casein, various surfactants, metal oxides, and the like. Amongthem, the delamination layer particularly desirably comprises: solely anacrylic resin having a molecular weight on the order of 20,000 to100,000, or combinedly the acrylic resin and a vinyl chloride-vinylacetate copolymer resin having a molecular weight of 8,000 to 20,000;and 1 to 5 wt % of a polyester resin having a molecular weight of 1,000to 5,000 as an additive.

Further, it is desirable for the delamination layer to exhibit adelamination force of 1 to 5 g/inch (90° delamination) between thesubstrate film and volume hologram layer. Further, its thickness isdesirably within a range of 0.1 μm to 2 μm, from a standpoint ofdelamination force, foil cutting, and the like.

Moreover, the reflective layer is to be formed between thethermo-sensitive adhesive layer and the volume hologram layer, such thatusage of metal thin-film or the like as the reflective layer results inan opaque type of hologram, and usage of a transparent substance havinga refractive index difference with that of the volume hologram layerresults in a transparent type of hologram, which are both usable in thepresent invention. Such a reflective layer can be formed by a knownmethod such as sublimation, vacuum vapor deposition, sputtering,reactive sputtering, ion plating, electroplating, and the like.

Examples of metal thin-films for forming an opaque type of holograminclude those thin-films to be formed from a single kind or combined twoor more kinds selected from metals consisting of Cr, Ti, Fe, Co, Ni, Cu,Ag, Au, Ge, Al, Mg, Sb, Pb, Pd, Cd, Bi, Sn, Se, In, Ga, Rb, and thelike, and oxides, nitrides, and the like thereof. Among the metalthin-films, Al, Cr, Ni, Ag, Au, and the like are particularlypreferable, and it is preferable that its film thickness is within arange of 1 to 10,000 nm, preferably within a range of 20 to 200 nm.

Contrary, usable as a thin-film for forming a transparent type ofhologram are any materials insofar as the same are light transmissibleto thereby exhibit a hologram effect. For example, examples thereofinclude a transparent material having a refractive index different fromthat of the resin included in the volume hologram oriented resincomposition. In this case, the refractive index of the former may belarger or smaller than the refractive index of the resin included in thevolume hologram oriented resin composition, and the refractive indexdifference is preferably 0.1 or more, more preferably 0.5 or more, andoptimally 1.0 or more. Additionally to the above, the examples include ametallic reflective film of 20 nm or less, and examples of preferablyusable transparent type reflective film include titanium oxide (TiO₂),zinc sulfide (ZnS), Cu.Al complex metal oxide, and the like.

It is further possible to provide a barrier layer either or both betweenthe delamination layer and the volume hologram layer, and between thevolume hologram layer and the thermo-sensitive adhesive layer. Dependingon combinations of the volume hologram oriented resin composition,delamination layer, and thermo-sensitive adhesive layer to be used inthe present invention, migration of low molecular weight components mayoccur over time from the volume hologram layer into the other layer, andas a result thereof, the peak wavelength of the recorded hologram mayshift to a blue side (shorter wavelength side), or the delaminationproperty may be changed when such components have migrated into thedelamination layer or the like. Provision of the above barrier layerenables such an obstructive factor to be overcome.

Materials to be used as such a barrier layer are not particularlylimited insofar as the same exhibit a barrier property, and usually,adoption of a transparent organic resin material enables achievement ofthe purpose. Among others, it is possible to use a non-solvent type 3 ormore functional, preferably 6 or more functional ionizingradiation-curing epoxy denatured acrylate resin, urethane denaturedacrylate resin, acryl denatured polyester resin, and the like which arereactive to ionizing radiation such ultraviolet light, electron beam,and the like. Particularly, there is preferably used a urethanedenatured acrylate resin among them, because of its high barrierproperty.

Further, preferably usable as the ionizing radiation-curing resin arethose having a molecular weight in a range of 500 to 2,000 in view ofits coating suitability, hardness of an eventually obtained barrierlayer. Moreover, the coating of the barrier layer is basically free ofsolvent, so that it can be formed laminatedly on any one of the volumehologram layer, delamination layer, and thermo-sensitive adhesive layer.

Meanwhile, it is possible to form an adherence improving layer, in caseof weak cohesion forces between respective layers.

Although the hologram transfer foil of the present invention may beproduced by successively laminating the substrate film, the volumehologram layer, and the thermo-sensitive adhesive layer, it can also beproduced by preparing the respective members in independent processes,and by subsequently laminating them.

Examples thereof include a method for preparing a volume hologram layerincluding an image recorded therein, a substrate film formed with adelamination layer, and a thermo-sensitive adhesive layer, and forlaminating them. Preparing the respective members in independentprocesses enables formation of the delamination layer on the substratefilm by a dry process, for example, thereby allowing adoption of variousmaterials, an improved production efficiency, and the like.

Further, it is also exemplarily possible: to prepare a member obtainedby forming a volume hologram layer on a substrate film (which may beformed with a delamination layer thereon) and subsequently recording animage in the volume hologram layer, and a thermo-sensitive adhesivelayer; and to laminate them with each other. In this case, to be coatedonto a supporting body is a composition for forming the volume hologramlayer, followed by irradiation of laser or the like to therebypolymerize a radical polymerizable compound to record an image therein,and then the composition and supporting body are laminated onto thesubstrate film. Thereafter, irradiation is conducted over the wholesurface of the volume hologram oriented resin composition, therebyforming a member including the volume hologram layer having the imagerecorded therein and the substrate film laminated thereon. Subsequently,the supporting body is peeled off, and a thermo-sensitive adhesive islaminated while heating at 100° C. to 180° C., for example, to therebycomplete a due method.

Here, the above-mentioned volume hologram layer of the present inventionis applicable to a plastic card, cellular phone, premium ticket,commodities, CD-ROM package, and the like.

Further, the present invention also embraces a method for controlling aninter-layer adhesive force between the substrate film and the volumehologram layer.

Namely, in case that the layer constitution of the hologram transferfoil of the present invention has a delamination layer, it is preferableto satisfy: the following relative relationship among an inter-layeradhesive force A between the delamination layer and substrate film, aninter-layer adhesive force B between the delamination layer and volumehologram layer, and an inter-layer adhesive force C between the volumehologram layer and thermo-sensitive adhesive layer; and the value of B:

Inter-layer adhesive force: C≧B>A

B value: 600 gf/inch

There will be next explained laser marking of the volume hologram layer.

Examples of laser types for marking include far infrared laserrepresented by CO₂ laser, visible light pulse laser, near infrared pulselaser represented by Nd:YAG laser, Nd:YVO laser, excimer laser,ultraviolet laser utilizing third-harmonics of Nd:YAG laser or Nd:YVOlaser, semiconductor laser, femto-second laser, pico-second laser, andthe like. Particularly, advantages of Nd:YAG laser and Nd:YVO laserinclude a higher output and higher pulse-stability, and the like.Further, advantages of the laser utilizing third-harmonics of Nd:YAGlaser or Nd:YVO laser include a higher resolution, UV lightabsorbability, and the like. Moreover, ultrashort pulse laser such asfemto-second laser, pico-second laser and the like is capable of cuttinga bond between molecules of a material without bringing it into a hightemperature state, thereby allowing nonthermal writing.

Examples of marking laser include the following:

Near infrared laser: “VECTOR” manufactured by Coherent, Inc.

wavelength: 1,064 nm

averaged output: 0.75 to 3 W or more

pulse width: 10 to 100 ns or longer

Ultraviolet laser: “AVIA Ultra” manufactured by Coherent, Inc.

wavelength: 355 nm

averaged output: 1 to 2 W or more

pulse width: 25 ns or longer

Ultraviolet laser: “Paladin” manufactured by Coherent, Inc.

wavelength: 355 nm

averaged output: 4 to 8 W or more

pulse width: 15 ps or longer

Ultrashort pulse laser: “Mira” manufactured by Coherent, Inc.

wavelength: 700 nm to 980 nm

averaged output: 0.65 to 1.3 W or more

pulse width: 200 fs or shorter

Further, typical marking includes irradiating laser to a volume hologramlayer to cause carbonization or the like thereof at high temperature byabsorption of an energy of laser pulses, thereby recording information.Upon carbonizing a plastic material by laser light, the followingconditions are required:

Irradiation energy: 0.2 to 5.0 mJ

Irradiation pulse power: average of 1 kW or more

Irradiation laser power: 3 to 20 W

Pulse width: Information is satisfactorily recorded by using short pulselaser of 3 pico-second to 30 femto-second. Particularly, 10 pico-secondto 10 femto-second is desirable.

The laser is used toward the substrate by which the hologram transferfoil has been transferred to a card material or before suchtransference, to modify the volume hologram layer by virtue of thefollowing effects to exhibit contrast so that information is writtenthereinto.

Physical Effects

Carbonization/melting/ablation (engraving) of material by heat:Interference fringes recorded in the hologram at a marking portion arecompletely broken.

Laser marking into the target material is possible, without particularlyadding a dopant into the volume hologram layer.

Only, addition of a dopant enables improvement of a marking property.

Examples of a dopant include the inorganic materials as described above(for example, it is possible to use titanium dioxide, mica, and the likeeach having a surface coated with anthracene or pentaerythritol, asdisclosed in the Patent Document 4).

Chemical Effects

Structural change of used material due to heat or light: Breakage ofinterference fringes at a marking portion is almost absent, and markingis achieved by alteration of an added substance as follows:

For example, there is previously added a material: photochromicmaterial, pigment, which has a refractive index (structure) to bechanged by light irradiation.

Although there is required a strong irradiation energy for obtainment ofthe above-mentioned physical effects, marking is possibly readilyachieved by addition of a material such as a photochromic materialhaving a refractive index to be changed by light.

Usable examples of pigment include the above-mentioned sensitizingpigment, and it is required in such a case to shift a hologram recordingwavelength from a laser marking wavelength.

Existent as pigments are numerous compounds having various absorptionwavelengths from an ultraviolet region to an infrared region.

By virtue of the physical effects and chemical effects as describedabove, there is achieved a contrast between a laser light irradiatedportion and a non-irradiated portion.

1. The hologram layer is modified or broken by carbonization, melting,ablation, or the like thereof, so that the hologram layer is brought toinclude information recorded therein having a bright/dark contrastbetween an irradiated portion and a non-irradiated portion.

2. The hologram layer is modified through an inorganic material ororganic material contained in the hologram layer by heat, energy, light,or the like of laser light, so that the hologram layer is brought toinclude information recorded therein having a bright/dark contrastbetween an irradiated portion and a non-irradiated portion.

Concerning Bright/Dark Contrast:

In case of carbonization: bright portion is hologram image; and darkportion is black.

In case of melting: bright portion is hologram image; and dark portionis less visible hologram image or substrate image.

In case of ablation: bright portion is hologram image; and dark portionis substrate image.

In case of refractive index modulation:

Enhancement=bright portion is more visible hologram image (irradiatedportion); and dark portion is hologram image (non-irradiated portion).

Reduction=bright portion is hologram image (non-irradiated portion); anddark portion is less visible hologram image (irradiated portion).

In case of photochromic material: bright portion is hologram image; anddark portion is color change.

There will be explained an irradiation method of laser light for markingto a volume hologram layer. Although it is possible to adopt a methodfor directly irradiating laser light to a hologram layer through a maskor the like for selective irradiation of laser light to the hologramlayer, it is desirable to condense laser light to be irradiated so as toincrease an energy density to thereby attain a higher resolution ofinformation to be provided to the volume hologram layer. Such asituation is shown in FIG. 5. Laser light 10 from laser 8 is condensedby a condenser lens 9 in a manner that a volume hologram layer 2including a volume hologram recorded therein is positioned near a lightcondensation point, so that recording is conducted by changing thevolume hologram layer into a modified region 11 near the lightcondensation point. For recording of a desired pattern, it is enough torelatively scan the volume hologram layer by a condensed beam of thelaser light 10 while modulating the same. This laser light irradiationmay be conducted in a state of the transfer foil (FIG. 1, FIG. 3, andFIG. 4), in a state after transference thereof onto the adherend 6 (FIG.2), or in a state of hologram film before provision of the substratefilm (protective layer) 1.

Note that, in case of irradiating laser light 10 in a condensed mannerafter transference of the volume hologram layer 2 onto the adherend 6 asshown in FIG. 5, the visibility of marking is further improved bysimultaneously modifying not only the volume hologram layer 2 but also aplastic surface of the adherend 6 under it. FIG. 5 shows a modifiedregion 11′ of the adherend 6.

The present invention may also be configured as follows.

The film containing the previously described photo-polymerizablecompound is laminated onto a volume hologram layer, and laser light isirradiated thereto. The compound is thermally diffused into the hologramlayer at an irradiated portion by virtue of heat and light of the laserlight, and is further photo-polymerized, stabilized, and marked into thehologram layer.

Further, there is added a compound into a heat sealing layer ordelamination layer adjacent to the hologram layer in the constitution ofthe hologram transfer foil, and the compound is migrated into astabilized hologram layer by virtue of heat and light of laser light,and is further photo-polymerized, stabilized, and marked into thehologram layer.

EXAMPLES

There will be concretely explained the laser marking hologram of thepresent invention by Examples.

Example 1

There was prepared a volume hologram oriented resin composition of thefollowing formulation.

Polymethyl methacrylate (weight- 100 parts by weight average molecularweight 200,000) 2-phenoxy ethylacrylate 120 parts by weight 2-ethoxyethylacrylate 120 parts by weight Hexaallylbiimidazole 10 parts byweight 2,5-bis[4-(diethylamino)-phenyl]- 1 part by weightmethylene-cyclopentanone 1-butanol 100 parts by weight Methyl ethylketone 100 parts by weight

Coated onto a 50 μm polyethylene terephthalate (PET) film (Lumirror T60manufactured by Toray Industries) was a volume hologram oriented resincomposition, so as to attain a film thickness of 10 μm after drying,thereby obtaining a volume hologram formation layer. As shown in FIG. 6,this volume hologram formation layer was closely contacted with a mirrormaster, and argon ion laser light (wavelength 514.5 nm) was injectedfrom a side of the PET film at 35° relative to a normal line, therebycausing interference between incident light and reflected light torecord a volume hologram (hologram mirror). Further, the volume hologramwas provided in a stabilized state by heating and by developmentexposure to ultraviolet light.

The thus obtained hologram was subjected to irradiation of condensedlaser light by “AVIA Ultra” manufactured by Coherent, Inc., therebyconfirming a change of contrast of the hologram (modification bycarbonization). This resulted in a volume hologram having a highersecurity by virtue of provision of individualized information.

Example 2

There was prepared a volume hologram in the same manner as Example 1,except that the volume hologram recording resin composition of Example 1was changed as follows:

Volume hologram recording resin composition: Polymethyl methacrylate(weight- 100 parts by weight average molecular weight 200,000)9,9-bis(4-acryloxy- 80 parts by weight diethoxyphenyl)-fluorene1,6-hexanediol glycidyl ether 70 parts by weight Diphenyl iodoniumhexafluoro 5 parts by weight antimonate 3,9-diethyl-3′-carboxylmethyl- 1part by weight 2,2′-thiacarboxyanine iodine salt 1-butanol 100 parts byweight Methyl ethyl ketone 100 parts by weight

There was irradiated laser light in the same manner as Example 1,thereby confirming a change of contrast of the hologram (modification bycarbonization). This resulted in a volume hologram having a highersecurity by virtue of provision of individualized information.

Examples 3 and 4

There were prepared volume holograms in the same manner as Example 1,respectively, except that the volume hologram recording resincomposition of Examples 1 and 2 each included 20 parts by weight oftitanium dioxide having an averaged particle size of 300 nm as a lasermarking compound added in the composition. As a result of laser markingof individualized information in the same manner as Example 1, therewere obtained volume holograms each having a higher security(modification by heat melting).

Example 5

The volume hologram layer of Example 4 was used to prepare a hologramtransfer foil in the following manner.

Coated onto a PET film (Lumirror T60 manufactured by Toray Industries)having a thickness of 25 μm was a delamination layer formation materialof the following formulation, so as to attain a film thickness of 1 μmafter drying, thereby preparing a combination of delamination layer/PET.

Polymethyl methacrylate (weight- 97 parts by weight average molecularweight 35,000) Polyethylene wax (weight-average 3 parts by weightmolecular weight 10,000) Polyester (weight-average 0.3 parts by weightmolecular weight 1,500) Methyl ethyl ketone 200 parts by weight Toluene200 parts by weight

(Preparation of Thermo-Sensitive Adhesive Layer/Separation-Treated PET)

Coated onto a separating agent treated PET film (SP-PET manufactured byTOHCELLO Co., Ltd.) was the following thermo-sensitive adhesive layerforming material so as to attain a film thickness of 3 μm after drying,thereby preparing a thermo-sensitive adhesive layer/separation-treatedPET.

Ethylene-vinyl acetate copolymer resin solution (AD1790-15 manufacturedby Toyo Morton Ltd.)

(Preparation of Hologram Transfer Foil)

Laminated onto a hologram surface of a volume hologram layer/PETseparated from a mirror master, was a delamination layer surface of adelamination layer/PET at 80° C., thereby obtaining a laminated bodycomprising a PET/delamination layer/volume hologram layer/PET. Next, thePET laminated on the volume hologram layer was separated from thelaminated body, and the thermo-sensitive adhesive layer of the aboveobtained thermo-sensitive adhesive layer/separation-treated PET waslaminated onto the hologram surface at 130° C., followed by separationof the separation-treated PET from the thus obtained laminated body,thereby obtaining a hologram transfer foil comprising a PET/delaminationlayer/volume hologram layer/thermo-sensitive adhesive layer.

(Transference of Hologram, and Marking)

The thermo-sensitive adhesive layer surface of the obtained hologramtransfer foil was mated with a vinyl chloride card as an adherend, and adie heated to 150° C. was pressed onto the foil from the PET side,thereby transferring the hologram to the adherend. Further, there waswritten individualized information by laser marking in the same manneras Example 1, thereby enabling preparation of a hologram transferredcard having a higher security. Moreover, there was achieved an excellentfoil cutting property upon transference, by virtue of addition oftitanium dioxide particles.

Note that the present invention is not limited to the above describedembodiments and Examples. The embodiments and Examples are merelyillustrative, and whatever has the substantially same constitution andexhibits the same functions and effects as the technical concept recitedin claims of the present invention, are embraced within the technicalscope of the present invention.

1. A laser marking hologram comprising a volume hologram layer includinginterference fringes recorded therein, wherein said volume hologramlayer includes at least one of information of character, numericalcharacter, picture pattern, biometric matter recorded therein, saidvolume hologram layer further having a contrast between an irradiatedportion and a non-irradiated portion thereof provided by selectivelyirradiating laser light to said volume hologram layer, said volumehologram layer formed from a resin composition, the resin compositionincluding a radical photo-polymerizable compound, a cationicphoto-polymerizable compound, and a photopolymerization initiator,wherein: a refractive index of the radical photo-polymerizable compoundis greater than a refractive index of the cationic photo-polymerizablecompound, said resin composition further including photochromiccompounds, and the photochromic compounds are selected from the groupconsisting of chromene based compounds, spirooxazine based compounds,spirogyran based compounds, fulgide based compounds, and azobenzenebased compounds.
 2. A laser marking hologram comprising at least: aprotective layer; a volume hologram layer comprising a hologram filmmedium including interference fringes recorded therein; and a heatsealing agent or adhesive agent, wherein said volume hologram layerincludes at least one of information of character, numerical character,picture pattern, biometric matterrecorded therein, said volume hologramlayer having a contrast between an irradiated portion and anon-irradiated portion thereof provided by irradiating laser-light tosaid volume hologram layer to thereby modify said volume hologramlayer-, wherein said volume hologram layer formed from a resincomposition, the resin composition including a radicalphoto-polymerizable compound, a cationic photo-polymerizable compound,and a photopolymerization initiator, wherein: a refractive index of theradical photo-polymerizable compound is greater than a refractive indexof the cationic photo-polymerizable compound, said resin compositionfurther including photochromic compounds, and the photochromic compoundsare selected from the group consisting of chromene based compounds,spirooxazine based compounds, spirogyran based compounds, fulgide basedcompounds, and azobenzene based compounds.
 3. The laser marking hologramof claim 1 or 2, characterized in that the laser for irradiating thelaser light is configured to oscillatingly generate ultrashort pulseswithin a range of 10 pico-seconds to 10 femto-seconds.
 4. The lasermarking hologram of claim 1 or 2, characterized in that the laser forirradiating the laser-light is adapted for an ultraviolet region.
 5. Thelaser marking hologram of any one of claim 1 or 2, characterized in thatsaid irradiated portion is modified by condensing the laser light intosaid volume hologram layer.
 6. A card with the laser marking hologram ofany one of claim 1 or 2, the laser marking hologram comprisinginformation recorded therein by irradiating the laser light to thevolume hologram layer in a manner to modify the volume hologram layer,characterized in that said volume hologram layer includes individualizedinformation recorded therein by irradiation of the laser light.
 7. Acard with the laser marking hologram of any one of claim 1 or 2, thelaser marking hologram comprising information recorded therein byirradiating the laser light to the volume hologram layer in a manner tomodify the volume hologram layer, characterized in that said volumehologram layer includes the interference fringes recorded therein as ahologram having a function for diffracting or transmitting specificlight, and that said volume hologram layer includes individualizedinformation recorded therein by irradiation of the laser light.
 8. Alaser marking hologram-transferred body having the laser markinghologram of any one of claim 1 or 2, the laser marking hologramcomprising information recorded therein by irradiating the laser lightto the volume hologram layer in a manner to modify the volume hologramlayer, characterized in that said volume hologram layer includesindividualized information recorded therein by irradiation of the laserlight.
 9. A laser marking hologram-transferred body having the lasermarking hologram of any one of claim 1 or 2, the laser marking hologramcomprising information recorded therein by irradiating the laser lightto the volume hologram layer in a manner to modify the volume hologramlayer, characterized in that said volume hologram layer includes theinterference fringes recorded therein as a hologram having a functionfor diffracting or transmitting specific light, and that said volumehologram layer includes individualized information recorded therein byirradiation of the laser light.
 10. A volume hologram transfer foilcharacterized in that said volume hologram transfer foil comprises, in alaminated manner, at least: a substrate; a laser marking hologramcomprising a volume hologram layer, said laser marking hologramincluding information recorded therein by irradiating laser light to thevolume hologram layer including interference fringes recorded therein ina manner to modify said volume hologram layer; and a heat sealing agentor adhesive agent, wherein: said volume hologram layer formed from aresin composition, the resin composition including a radicalphoto-polymerizable compound, a cationic photo-polymerizable compound,and a photopolymerization initiator, a refractive index of the radicalphoto-polymerizable compound is greater than a refractive index of thecationic photo-polymerizable compound, said resin composition furtherincluding photochromic compounds, and the photochromic compounds areselected from the group consisting of chromene based compounds,spirooxazine based compounds, spirogyran based compounds, fulgide basedcompounds, and azobenzene based compounds.
 11. A laser markinghologram-transferred body, characterized in that said laser markinghologram-transferred body comprises a medium having said volume hologramtransfer foil of claim 10 transferred thereon.
 12. The laser markinghologram-transferred body of claim 11, characterized in that said mediumis in a form of card, that said volume hologram layer includes theinterference fringes recorded therein as a hologram having a functionfor diffracting/transmitting specific light, and that said volumehologram layer includes individualized information recorded therein byirradiation of the laser light.